Conversion of solid fuels and products derived therefrom or other materials into valuable liquids



Dec. 6, 1932. c. KRAUCH ET AL 1,890,436 CONVERSION OF SOLID FUELS AND PRODUCTS\ DERIVED THEREFROM OR OTHER MATERIALS INTO VALUABLE LIQUIDS Original Filed Feb. 6, 1926,

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N E 1 1 g Q I Q T i Q 1 Q L N illif' 395M x T 2 +1 Kg 1 5 inventors 6/4/71. fifiwuch /7/777//,q5 7 /5 Patented Dec. 6, 1932 UNITED STATES PATENT OFFICE.

CARL KBAUCH, OF LUDWIGSHAFEN-ON-THEJRHINE, AND HA'I'HIAB PIER, OI H'EIDEIev' BERG, GERMANY, ASSIGNOBS, BY MESN IPANY, OF LIND EN, NEW JERSEY, A CORPORATION OF DELAWARE conversion on son!) FUELS Ann raonno'rs n'nmvnn rrnnnnraon on ornna mnrnnmrs m'ro VALUABLE mourns Original application filed February 8, 1928, Serial No. 86,646, and in- Germany February 16, 1925.

Divided and this application filed April- 7,

One of the most important and widely agitated problems in the industrial world has for a long time been how to produce 00d gasoline or other valuable liquid'fuels roin solid .fuel including coal in all its vari-' eties and wood, and products'of distillation ormineral oils especially heavy oils.

One attempt at the solution of this problem has beenmade by-the so-called liquefaction of coals by means of hydrogen or by destructive hydrogenation of tars or oils at a hi h pressure and high temperature but this has not reached a plication industrially because of an unsatis actory speed and rate of the conversion.

By the process described in the specification 'of the original application No. 86,646

filed February 6th 1926, of'which this is a division, we claim to have successfully solved this problem for the first time and to be able to produce good pure liquid fuels, including also benzines from solid fuels and to convert also tars obtained from solid fuels and also heavy mineral oils, or crude oilsi or residues mto more valuable liqui products, including benzines, by a process economical in material,'time, labour and wear of the apparatus.

In arriving at this result we have made several discoveries or inventions to certain of which this a plication is directed.

We have found that among the many possible applications or modifications of the process in accordance with our parent application Ser. No; 86,646 particularly excellent results are obtained by the treatment of liquid fuels, namely distillation products of coal, lignite and other solid fuels, whether ordinary or primary (from low temperature .carbonization) or other tars or crude min- .eral 011s and their fractions or products obtained from these by various industrial treatments, all of which products we" comrise by the term crude liquid hydrocarons, with hydrogen in the, presence of a catalyst containing a metal of the sixth group of the periodic system (whether as .such or in a combined condition) give particularly valuable results. By the term metals of the sixth aroma of the nerin'rlin as...

1927. Serial No. 181,883.

we mean molybdenum, tun sten, chromium and uranium. We have f iiund that such catalysts are not poisoned by the sulfur compounds and other impurities contained in said materials and are highly eflicient for a very great length of time. The treatment with hydrogen is best carried out under a pressure of about 50 or more atmospheres and most advantageously the material to be treated is vaporized or sprayed or otherwise finely divided and carried with hydrogen over the said catalyst containing any of the said metals, or an oxidor other compound thereof under a pressure of a suitable range, and at an elevated temperature suflicient for promoting the reaction, generally ranging between about 300 and 700 C.

'By the said treatment, the original material Tis split up into smaller molecules which partly may recombine to form products of a higher order or at least the sulfur compounds contained therein are destroyed with an evolution of gaseous sulfur compounds, and at the same time oxygen compounds and unsaturated bodies contained the ein or formed by the splitting process are reduced and hydrogenated, the whole of which transformations we designate a destructive hydrogenation. In order to avoid an attack of the apparatus by sulfur or other influences, which is' a seriousdifiiculty in the practical perform ance of the process, we have found it excellently suitable to compose or line the apparatus where it comes into contactwith hot gaseous,liquid or solid carbonaceous material, of aluminium or its alloys which metals may be used until near their melting point. Also chromium and its alloys prove very resistant to corrosion in the course of'the operation and withstand also all temperatures E ASSIGNMENTS, TO STANDARD-I. G. COH

which may come into question. Especially bon, are very suitable. At the same time a content of nickel amounting to 40 percent by sulphur for the present process may contain for example, molybdenum or its compounds, such as sulfids, or molybdic acid, or molybdates of ammon um or. other bases, or other metals of the aforesaid group or them compounds, and other substances, immune from poisoning by sulphur, whether possessing hydrogenating properties, or not, may be admixed thereto- For example, cobalt or iron, or compounds thereof, or alumina, zinc oxid, magnesia, or calcium carbonate, may be clted as admixtures. Sup orts, forexample, lum s of clay may also e used.

The pre erred form of carrying out the process is generally a continuous operation with a stream of the gases and the materials finely divided therein, and with an excess of hydrogen over the required quantit; and preferably while maintaining the esired pressure b adding fresh gas and passing the gas either y circulation through one or more I reaction vessels, or through a succession of 85 reaction vessels, without circulation. The

products are separated from the reaction gases by cooling or absorbing with a wash oil or solid adsorbents or in any suitable manner.

The gases serving for the .reaction may consist of h drogen alone or of mixtures containing hy rogen, for example a mixture of hydrogen and nitrogen or water gas, or hydrogen mixed with car on dioxid, hydro en sulfid, water vapor, or methane orot er hydrocarbons. Or the hydrogen may be gen-.

erated in the reaction chamber by the interaction of water and carbon monoxide or the like; or by decomposing the gaseous hydrocarbons formed during the treatment, and to be found in the reaction gases, by burning with a restricted quantity of oxygen so as to combine substantially with the carbon to form carbon monoxide and liberate hydrogen. Or the aseous hydrocarbons may be decomposed w1th steam at a high temperature or with mixtures of water vapor and oxygen.

Catalysts may be employed for facilitating said decomposition, for example, nicke coated magnesia or other solid bodies, a melt of iron or iron alloys or other catalysts for the reaction. The decomposition may take place either at ordinary pressure or, when oxygen is employed, under a pressure identical with that prevailing in the destructive names reaction temperature ranges between 300 and 700 C. and the pressure may amount to 20, 50 200 or still more atmospheres.

The liquid hydrocarbons obtained are enerally very low in sulfur or free thererom, and are excellently suitable for use as fuel for internal combustion engines, or as lubricating oils, inasmuch as the are prodnets of a higher boiling point. T e low boilmg fractions may be mixed with other fuels, for example, benzines or ordinary gasoline, benzol, or low alcohols of the aliphatic series and possess the remarkable pro erty of being misc ble to a large degree with the latter, part cularly with methanol. A mixture contam ng 60 per cent of a hydrocarbon obtained from crude oil in accordance with the described process, 30 per cent of gasoline and 10 per cent of-methanol may be cited as an example. The products are also excellent solvents for a great variety of bodies.

In the accompanying drawing, an apparatus for carrying out the process accordin to the present invention is illustrated diagrammatically, part1 in vertical section. Qur lnvention is not limited to the apparatus illustrated therein, however, but may be varied at will in accordance with the conditions of working. T

Referring to the drawin in detail, refer-- ence numeral 1 indicates a eed line from an convenient source of liquid raw material: The line 1 discharges to a grinding mechan1s m 2 fitted with a hopper 3 throu h which sohd materials ma be admitted, i desired. Thegrinding mechanism can be by-passed biy line 1a when no solid materials are used.

he liquid may be then forced by pump 5 through a line 4 to a heat exchanger 6 and thence by line 7 into a reaction chamber 8.

The reaction chamber is constructed in any preferred manner and should be adapted to withstand high pressures, for example; above 20-100 or even as high as 800 atmospheres, as well as the corrosive effects of the reactants. The vessel is preferably protected from loss of heat by a suitable insulating cover 9 and may be heated by electric coils 10 which are arranged within the drum. The contents of the drum are preferably kept in astate of agitation by means of a stirring mechanism 11 and, if desired, suitablegcatalytic materials 11 as indicated above may be attached to the stirring mechanism so that the catalyst 1:0

is brought int'oiihimate contact with the contents of the vessel. a

Hydrogen under high pressure 1S forced through a line 12, heat exchanger 13 and then by line 14 into the base of the reactor 8 mto which it is preferably discharged through a spray pipe 15. A liquid level may be mamtained in the drum, for example at the point 16a and gas and vaporous products may be continuously withdrawn by vapor line 16 which is in communication with exchanlger 13 and a cooling coil or condenser 17 he condensate and gas is dischar ed -1n to a separation drum18 from which t e distillate is removed by line 19 to storage, not shown.

Y The as may be taken oil by a pipe 20 to a the as.

puri ying system indicated at 21, and which may comprise a scrubbing, system preferably carried out at high pressure usm for example, soda to remove hydrogen sulfi e and oil to'remove h .drocarbon constituents from Puri ed gas is then recompressed by a booster pump 22 and is forcedagain into the hydrogen feed line 12. Fresh hydrogen may be introduced by line 23.- If desired, 011 may be continuously removed from the drum by a line 24 which communicates with heat exchanger 6 and which is withdrawn to storage, not shown, by a suitable lme 25. If it is intended to carry out the destructlve hydrogenation according to the present invention in the vaporous phase the apparatus shown-in the accompanying drawing) needs only little modification. Thus the opper 3 may be dispensed with, and the initial liquid or vaporous hydrocarbon to be con: I 'verted is introduced at 1. Similarly lines 24 and 25 as well as the heat exchanger 6 may dispensed with. Between pump 5 and the entrance of line 7 into the reaction chamber a, a preheater is inserted in which the materials supplied at 1 are brought to the desired temperature and, if liquid, also vaporized.

This preheater may for example consist of a coil capable of being heated y combustion gases. In case of working in the va or phase no stirring mechanism is nee ed. The catalysts, therefore, may be employed in the form of solid pieces of any shape and of a suitable size, for example, that of hazel nuts filled into the reaction space. Y

In the following examples the time ofvreaction varies conslderably, as might bevsupposed, depending on the nature of the raw material, the activity of the catalyst, temperature, pressure and the like. In practice it is desirable to make a few reliminary runs in order to determine the time required for the best yields under a given set of conditions. Generally speaking, with batch operations the total time-may be from two to ten hours or more, depending on the yield desired, while with continuous operations the time is' usually shorter. When continually feeding liquid or difiicultly the rate of flow may be in the neighborhood of .3to .8 volumes of oil per hour per volume of reaction space. Vaporous materials may be treated at higher temperatures and the feed rate may consequent one and one-half volumes volume of reaction space.

r hour per e volume of hydrogen may likewlse vary considerably and should always, of course, be in excess of that actually required for the ,COIIYGISIOII;

may be in excess of about 600 litres per k1logram of carbonaceous material.

y be one or even The following'examples will serve to further explain how our invention is carried out in practice, but our invention is not re.- stricted to these examples,

Ewample] round in a circular way whi' e maintainmg' the pressure by an addition. of fresh hydrogen, and separating the material by coolin There is formed a thinand nearly co orles's product free from phenols, without any formation of coke, asphaltor other resi.

product distil up to 150 0., and the fractions up to 300 C. are colorless and fully saturated. At 350 degrees C. only a smal residue is left having a Vaseline-like nature. The raw product can be used as a motor fuel or for manufacturing lubricatin oils. tion of sa 1 per cent 0 ammonia to the hydrogen is also useful.

volume, of hydrogen and 25 per cent of nitrogen, may also be used, preferably at a pressure of 200 atmospheres.

Molybdic acid alone or molybdenum sulfid or other masses containing molybdenum may An 'addimixture consisting of per cent, byf

also'be em loyed, also coal tar, and comas raw cresylic acid.

Example 2 Raw cresylic acid obtained from coal tar is passed along with a current of hydrogen over tungstic acid under a pressure of 20 ponents suc 50Ql to 550 0'. whereby it is rapidly and completely converted into hydrocarbons.

' U Example? Petroleum residues when treatedas described in the foregoing example yield in a continuous manner and vaporizable oils, tion'of'coke" orasphalt,

without any formaat between 450 and atmospheres and at a. temperature of about T8 for example,-the rate ,of flow of hydrogen due. From thirty to fifty per cent of the percent of-benzineboiling up to 150.

' cally free from Example 4 Brown coal tar obtained ina as producer wit a mixtureis continually assed, along of 3 parts of ydrogen with one part (by volume) of nitro en at about 500 C. and under 200 atmosp eres over a contact mass consistingaof chromium hydroxid. The tar P is hereby converted into a thin oil, practiphenol and of a saturated nature and containing about 50 r cent of benzine boiling up to 150 0.). The fractions of hen boiling point are free from asphalt an can be converted into benzme by a-repeate'd treatment.

= Ezcample 6 v Dark-coloredresidues of an American rock oil which at ordinarytemperature are nearly solid andhave a} strongly unsaturatedcharof hydrogen and 1 part of nitrogen and continuously passed under a pressure 013.200 atmospheres and a temperature of from 450 to 500 C. over a contact mass pre ared from an intimate mixture of 70 parts, y weight,

.of ammonium .molybdate and parts of aluminiumhyr'oxid. A nearly colorless, thin andsaturated product is obtained besides a colorless gasoline boiling up to 150 and 10 er cent of a thin, yellowish product of a liigher boiling point.

Example 6' of a pitch-Ike residue over 350 C. is treated as described in the foregoing example. The

. product is a thin yellowish oil of 0.810 sp. gr.

containing 80 per cent of saturated gasoline boiling up to 150 and leaving at 200 C. a liquid weakly colored residue.

Example 7 Mexican asphalt is dissolved in its own weight of cyclohexane and treated in the aforedescribed manner. The cyclohexane is recovered unaltered, while the asphalt which before the treatment contained 4 per cent compounds boiling'up to 250 C., 25 per cent more boiling up to 350 C. and per cent of a hard pitch residue, is converted into a thin oil, 'free from oxygen compounds and chiefly consisting of gasoline hydrocarbons besides a very small Vaseline-like residue.

Rock oils of any origin may be treated as described in the above examples and thereby converted into refined products of much more valuable properties.

- with a gas mixture composed of 10 quantities.

nee s-so sam le a" v Vaporized brown coal tar is incorporated r cent,

by volume of'carbon'monoxid an 90 per cent of hydrogen and brought under a pressure of 200 atmospheres, and the mixture is passed. at about 450 C. over a contact mass prepared from 9 art of chromic acld. On cooling, a product is condensed which containssome methanol and oxygen compounds ofa higher order about er cent of benzine and products oi a higher oiling oint which may serve for a conversion into ubricating oils or for a repeated treatment as aforementioned. The

mixture of hydrogen and carbon monoxid is circulated while replacing the consumed ases.

In all of the above examples the'hot parts" acter are incorporated into an excess of a gas or made of or coated wlth an alloy of 60 per mixture composed of three parts, by volume,

cent of nickel, 27.7 per cent of iron, 12 per cent of chromium and 0.3 per cent of carbon;

arts of zinc oxid and 1 or .an alloy composedof 58 percent of nickel,

25 (percent of iron, 17 per cent of'chromium an 0.03 per cent of carbon; or an alloy composed of 96 per cent of iron, 1.7 5- per cent of nickel, 1.5 per cent of chromium, 0.1 per cent of carbon and also of 0.25 per cent of silicon, 0.2 per cent of manganese, besides small little methane consisting of 90 per cent of quantities of COppGflSUHur andlphosphorus' Our invention is not confined to the above examples; the conditions ma be Widely varied in various directions. or example the pressures and temperatures may be higher or lower than stated above.

In the appended claims, the expression liquid distillation products of solid fuels is intended to relate only to normally liquid distillation products and is not to be conv is used in said claims, it is not necessarily intended to mean that a catalyst is introduced into the reaction chamber with each charge of carbonaceous material, but is merely intended to indicate that the reaction is carried out in the presence of an effective quantity of a catalytic material whichis not naturally contained in the carbonaceous material undergomg treatment or is contained in said carbonaceous material in inefiective \Vhat we claim is:

hydrocarbons into a liquid rich in hydrocarbons of low boiling point of benzine character which comprises distributing the crude 1. The process of converting crude liquid liquid hydrocarbons in astream of hydrogen in excess of the required quantity and'exposing the mixture to heat at a temperature rangingbetween about 300 and 700 cent1- grade and a pressure upwards of 100 atmospheres, in the presencepf a catalyst comprising a metal of the sixth group of periodic system.

3. The process of converting crude l1qu1d hydrocarbons into a liquid rich in hydrocarbons of low boiling point of benzine character which comprises distributing the crude liquid hydrocarbons in a stream of hydrogen in excess of the required quantity and exposing the mixture to heat at a temperature ranging between about 300 and 700 centlgrade and a pressure upwards of 100 atmospheres, in the presence of a catalyst comprismg molybdenum.

4. The process of converting liquid d1stillation products of solid fuels into more valuable liquid hydrocarbons which comprises distilling a solid fuel in the presence of an introduced stream of added hydrogen and subjecting the evolved vapours to a treatment with hydrogen in excessof the required quantity and heat at a-temperature ranging betweenabout 300 and 700 centigrade and pressure of atleast 20 atmospheres in the presence of a catalyst comprising a metal of the sixth group of the periodic system.

5. The process of'converting crude liquid hydrocarbons into valuable liquid hydrocarbons which comprises destructively hydrogenating then. with added hydrogen and heat at a temperature ranging between about 300 and 7 00 centigrade in the presence of an added catalyst immune to-sulfur poisoning at a pressure of atleast 20 atmospheres.

6. The process of converting liquid d stillation products obtained from solid fuels into more valuable liquid hydrocarbons which comprises destructively hydrogenating them with added hydrogen and a catalyst comprising molybdenum and heat at'a temperature ranging between about 300 and 700 centigrade at an elevated pressure of at least 20 atmospheres. p

7 The process of converting liquid distillation products obtainedfrom solid fuels into'more valuable liquid hydrocarbons which comprises destructively hydrogenating them with added hydrogen and a catalyst containing a metal of the sixth group of the periodic system and a substance selected from the group consisting of alumina, zinc oxide, magnesia and calcium carbonate and heat at a temperature ranging between about 300 and 700 centigrade at an elevated pressure of at least 20 atmospheres.

8. The rocess of destructively hydrogenizing cru e liquid hydrocarbons which comp'rises'treating them with added hydrogen in the presence of an added solid catalyst imp'eratureabove 300 C. and at a pressure of at least 20 atmospheres, the conditlons of workiig such as temperature, pressure and the e ciency of the catalyst, be ng so adapted to each other asto give rise to the formation of f6 mune to sulfur poisoning and heat at a temsubstantial amounts of low boiling hydrocarbons of a benzine character. I

9. The process of converting crude liquid h'yldrocarbons -into more. valuableliquids w ich comprises destructivelyhydrogenatin 7 them with added hydrogen in the presence 0 an added solid catalyst immune to sulfur poisoning and heat at a temperature of 'between about 300 and 700 C. and at a pres-' sure upwards of 100 atmospheres.

10. The process of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenating them with a stream of added hydrogen and an added catalyst immune to sulfur poisoning and heat at a temperature of between about 300 and 700 C. and at an elevated pressure of at least 20 atmospheres.

11. The process of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenating them with added hydrogen and a catalyst comprising a metal of the sixth group of the periodic system and heat at a temperature of'betwe'en about 300 and 700 C. and at a pressure of at least 20 atmospheres.

12. The process of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenating them with added-hydrogen and a catalyst containing molybdenum .at a temperature upwards of 350 C.

13. The process of destructively hydrogenizing crude liquid hydrocarbons containing asphalt which comprises treating them with added hydrogen in the presence of an added solid catalyst immune to sulphur poisoning,

at a temperature above 300 C. and at a pressure-of at least 20 atmospheres for a period such that, under the conditions as above given. the

asphalt. 4

14. The process of converting crude liquid hydrocarbons into valuable liquid hydrocarbons. which com rises destructively hydrogproduct is substantially free from enating them with added hydrogen ata temperature ranging between about 300 and 700 centigrade in the presence of an added catalyst comprising an oxide of a-metal of group six of the periodic system and under a pressure of at least 20 atmospheres.

15. The process of converting crude li uid hydrocarbons into valuable l1 uid hy rocarbons which comprises destructlvely hydrgenating them with added hydrogen at a temperature ranging between about 300 and 700 centigrade in the presence of an added catalyst comprising an oxide of molybdenum and under a pressure of at least atmospheres. 4

16. The process of converting li uid distillation products obtained from so id fuels into more valuable liquid hydrocarbons which comprises destructively hydrogenating them with added hydrogen and a catalyst comprising ametal of the sixth group of the periodic system and a metal selected from the group consisting of cobalt and iron and heat at a temperature ranging between about 300 and 700 C. at an elevated pressure of at least 20 atmospheres. Y

17. The process of converting crude li uid hydrocarbons into more valuable liqui s which comprises destructively hydrogenating them with added hydrogen in the presence of a catalyst comprising a compound of a metal of the sixth group of the periodic system at a temperature between about 300 and 700 C. and under a pressure ofat least 50 atmos pheres.

18. The process-of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenating them with added hydrogen in the presence of a catalyst comprising chromium at a temperature between about 300 and 700 C. and under a pressure of at least 50 atmospheres.

19. The process of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenating them with added hydrogen in the presence of a catalyst comprising a compound of chromium at a temperature between about 300 and 700C. and under a pressure of at least 50 atmospheres.

20. The process of hydrocarbons into more valuable liquids which comprises destructively hydrogenating them with added hydrogen in the presence of a catalyst comprising an oxide of chromium at a temperature between about 300 and 7 00 C. and under a pressure of at least 50 atmospheres.

21. The process of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenatingthem with added hydrogen in the presence of a catalyst comprising tungsten at a temperature between about 300 and 700 C.

converting crude liquid which comprises destructively hydrogenatin them with added hydrogen in the presence 0% a catalyst comprism a compound of tungsten'at a temperature 700 C. and under-a atmos heres.

'23. he process of converting crude liquid hydrocarbons into more valuable liquids which comprises destructively hydrogenatin them with added hydrogen in the presence 0 a catalyst comprising an oxide of tun en at a temperature etween about 300 and 00 C. and under a pressure of at least 50 atmospheres.

24'. The process of converting crude liquid hydrocarbons. into more valuable liquids which comprises destructively hydrogenating them with added hydrogen in the presence of a catalyst comprismg a compound of molybdenum at a temperature between about 300 and 700 C. and under a pressure of at least 50 atmos heres.

In testimony whereof we have hereunto set our hands.

l CARL KRAUCH. MATHIAS PIER.

pressure of at least 50 tween about 300 and I and under a pressure of at least 50 atmospheres.

22. The process of converting crude liquid hydrocarbons into more valuable liquids 

